EP1232138B1 - Verfahren zum reinigen von (meth)acrylmonomeren durch destillation - Google Patents

Verfahren zum reinigen von (meth)acrylmonomeren durch destillation Download PDF

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Publication number
EP1232138B1
EP1232138B1 EP00979736A EP00979736A EP1232138B1 EP 1232138 B1 EP1232138 B1 EP 1232138B1 EP 00979736 A EP00979736 A EP 00979736A EP 00979736 A EP00979736 A EP 00979736A EP 1232138 B1 EP1232138 B1 EP 1232138B1
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EP
European Patent Office
Prior art keywords
oxygen
distillation
process according
column
meth
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Expired - Lifetime
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EP00979736A
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English (en)
French (fr)
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EP1232138A1 (de
Inventor
Michel Fauconet
Stéphane Lepizzera
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
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Arkema SA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation

Definitions

  • the present invention relates to a method of purification of (meth) acrylic monomers, such as acrylic acid, by distillation.
  • NO gas has such properties.
  • this molecule is a stable radical that can stop the growth of macromolecular chains and has a sufficiently high vapor pressure to ensure a homogeneous distribution thereof in the medium.
  • this molecule reacts very rapidly with oxygen to form NO 2 , a molecule described in the literature as being able to initiate polymerizations.
  • FR-A-1,567,710 describes the use of NO gas, in the absence of oxygen, during the synthesis of (meth) acrylic derivatives.
  • FR-A-2 056 825 discloses the use of NO gas, in the absence of oxygen, and phenothiazine (liquid phase inhibitor) during the distillation of acrylic acid.
  • EP-A-301 879 discloses the use of a liquid phase inhibitor (phenolic compound / Mn or Ce salt) and a gas phase inhibitor which is either NO or the ammonium salt of the N-phenyl N-nitroso-hydroxylamine, during the distillation of monomers including acrylic acid.
  • US-A-4 338 162 which describes the use of nitrogen oxides, preferentially the nitric oxide in the absence of oxygen during distillation of cyanoacrylic esters.
  • the applicant company has therefore sought to resolve this stabilization problem, while maintaining a conventional stabilization of the liquid phase in particular by the use of inhibitors requiring an introduction oxygen.
  • the applicant company carried out distillation tests of acrylic monomers in the presence of NO 2 , which led it to observe that surprisingly, under certain operating conditions, the NO 2 gas, industrially interesting because it is less expensive than the NO gas, provides a stabilization during the distillation of the acrylic monomer, in other words acts as a gas phase inhibitor, while it is generally known as a polymerization initiator.
  • the above conditions consist of respecting, on the one hand, a certain oxygen / organic vapor ratio - the control of this parameter making it possible to optimize the stability of the liquid phase - and, on the other hand, a certain NO 2 ratio.
  • / organic vapor - the control of this parameter makes it possible to ensure an inhibitory efficiency of the NO 2 in the gas phase and to prevent the initiation of the polymerization.
  • this direct injection offers the complementary advantages of the greatest ease injection of a gas with respect to a liquid in a industrial distillation column and the improvement of industrial hygiene by injecting a gas rather than of a liquid.
  • the subject of the present invention is therefore a process for purifying a (meth) acrylic monomer chosen from (meth) acrylic acids and their esters by distillation in the presence of at least one polymerization inhibitor requiring an introduction of oxygen and or an inhibitor having a better efficiency in the presence of oxygen for the stabilization of the liquid phase, characterized in that the distillation is also carried out in the presence of NO 2 gas, with a ratio (w / w) oxygen / organic vapor between 0.02 and 3%, in particular between 0.04 and 0.5%, and with a ratio (w / w) NO 2 / organic vapor between 0.01 ppm and 50 ppm, in particular between 1 ppm and 30 ppm.
  • This assembly consists of a distillation column equipped with perforated trays spillway and a thermosiphon boiler, and surmounted by a gooseneck.
  • Organic vapors are condensed using a conventional refrigerant. Part of the condensed liquid is recycled to the top of the column after addition of liquid phase stabilizers.
  • the distillation is carried out under reduced pressure of 2.66 ⁇ 10 4 Pa (200 mmHg) with a temperature of 97 ° C. in the boiler and 87 ° C. at the top of the column.
  • the distillation is carried out for 24 hours. Polymers appear mainly at the level of two zones of condensation of organic vapors: the probe of stainless steel temperature of the column head and the flange of connection of the gooseneck to the refrigerant. At the end of the test these polymers are dried and weighed.
  • the flow used for all the tests presented is consisting of crude acrylic acid whose major impurity is acetic acid at 4% by weight. This flow feeds continuously the column to be distilled with a flow rate of 160 g / h. 69 g / h of distillate are withdrawn from the column and withdraws 91 g / h in the foot. The flow of organic vapor in the column is 335 g / h.
  • Condensed organic vapors (335 g / h) are stabilized with an acrylic acid solution containing 2% by weight of hydroquinone and 0.25% of dibutylthiocarbamate copper at a rate of 2.4 g / h. A fraction of these vapors condensed organic matter (266 g / h) is returned to the top of the distillation column.
  • the introduction of oxygen is carried out in the boiler at a rate of 0.21 l / h, a ratio (w / w) oxygen / organic vapor of 0.09%.
  • the introduction of gaseous NO 2 is carried out in the feed with a flow rate of 1.9 ml / h, which corresponds to a ratio (w / w) NO 2 on organic vapor of 12 ppm.
  • Example 2 This example was carried out under the same conditions as Example 1, but with a NO 2 gas flow rate of 0.8 ml / h.
  • the ratio (w / w) NO 2 on organic vapor is therefore 5 ppm.
  • the distillate is clear, limpid, and the total amount of polymer formed at the of the two condensation zones of the column is 0.5 g.
  • Example 2 This example was carried out under the same conditions as Example 1, but with a NO 2 gas flow of 3.9 ml / h.
  • the ratio (w / w) NO 2 on organic vapor is therefore 24 ppm.
  • the distillate is clear, limpid, and the total amount of polymer formed at the of the two condensing zones of the column is 3.2 g.
  • the distillate is clear, limpid, and the total amount of polymer formed at the of the two condensing zones of the column is 8.1 g.
  • Example 2 This example was carried out under the same conditions as Example 1, but with a flow of gaseous NO 2 of 10.1 ml / h.
  • the ratio (w / w) NO 2 on organic vapor is therefore 62 ppm.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (9)

  1. Verfahren zur Reinigung eines unter (Meth)acrylsäure und Estern davon ausgewählten (Meth)acryl-monomers durch Destillation in Gegenwart mindestens eines Polymerisationsinhibitors, der die Eintragung von Sauerstoff erfordert, und/oder eines Inhibitors mit besserer Wirksamkeit in Gegenwart von Sauerstoff im Hinblick auf die Stabilisierung der flüssigen Phase, dadurch gekennzeichnet, daß man die Destillation außerdem in Gegenwart von NO2-Gas mit einem Gewichtsverhältnis von Sauerstoff zu organischem Dampf zwischen 0,02 und 3% und einem Gewichtsverhältnis von NO2 zu organischem Dampf zwischen 0,01 und 50 ppm durchführt.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Destillation mit einem Gewichtsverhältnis von Sauerstoff zu organischem Dampf zwischen 0,04 und 0,5% durchführt.
  3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man die Destillation mit einem Gewichtsverhältnis von NO2 zu organischem Dampf zwischen 1 und 30 ppm durchführt.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß man die Destillation in einer Kolonne unter einem Druck von 1,33 x 103 bis 6,66 x 104 Pa (10 bis 500 mmHg) bei einer Temperatur von 60-200°C in der Destillationsblase und 40-100°C am Kopf der Kolonne durchführt, wobei der Strom von zu reinigendem Monomer kontinuierlich zugeführt wird.
  5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß man in die Destillationsblase Sauerstoff einträgt.
  6. Verfahren nach Anspruch 4 oder 5, dadurch gekennzeichnet, daß man gasförmiges NO2 in die Zuführung und/oder die für Flüssigkeit nicht zugänglichen Stellen der Kolonne einträgt.
  7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man ein unter Acrylsäure, Methacrylsäure, C1-C10-Alkylacrylaten und C1-C10-Alkylmethacrylaten ausgewähltes (Meth)-acrylmonomer reinigt.
  8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß man als Polymerisationsinhibitor, der die Eintragung von Sauerstoff erfordert, einen phenolischen Inhibitor wie Hydrochinon, Hydrochinonmethylether, Butylhydroxytoluol oder 2,4-Dimethyl-6-butylphenol und/oder einen Inhibitor mit besserer Wirksamkeit in Gegenwart von Sauerstoff wie Phenothiazin und Derivate davon, para-Phenylendiamin und Derivate davon, ein Metallthiocarbamat, wie Kupferdibutyldithiocarbamat, ein Übergangsmetallcarboxylat, wie Manganacetat oder ein stabiles Nitroxidradikal, wie 4-Hydroxytetramethylpiperidin-N-oxyl verwendet.
  9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß man den Polymerisationsinhibitor in einer Menge von 50 bis 2000 ppm, bezogen auf die am Kopf der Kolonne kondensierten organischen Dämpfe, einträgt.
EP00979736A 1999-11-24 2000-11-15 Verfahren zum reinigen von (meth)acrylmonomeren durch destillation Expired - Lifetime EP1232138B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9914777A FR2801306B1 (fr) 1999-11-24 1999-11-24 Procede de purification des monomeres (meth) acryliques par distillation
FR9914777 1999-11-24
PCT/FR2000/003172 WO2001038285A1 (fr) 1999-11-24 2000-11-15 Procede de purification des monomeres (meth) acryliques par distillation

Publications (2)

Publication Number Publication Date
EP1232138A1 EP1232138A1 (de) 2002-08-21
EP1232138B1 true EP1232138B1 (de) 2005-10-19

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EP00979736A Expired - Lifetime EP1232138B1 (de) 1999-11-24 2000-11-15 Verfahren zum reinigen von (meth)acrylmonomeren durch destillation

Country Status (9)

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US (1) US7029556B1 (de)
EP (1) EP1232138B1 (de)
JP (1) JP4131005B2 (de)
KR (1) KR100520266B1 (de)
CN (1) CN1220670C (de)
AU (1) AU1712901A (de)
DE (1) DE60023336T2 (de)
FR (1) FR2801306B1 (de)
WO (1) WO2001038285A1 (de)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002077504A (ja) * 2000-08-28 2002-03-15 Kyocera Mita Corp プッシュ型スキャナ装置およびその使用方法
FR2814741B1 (fr) * 2000-09-29 2004-02-27 Atofina Procede de stabilisation de monomeres acryliques
WO2003031384A1 (en) 2001-10-09 2003-04-17 Mitsubishi Chemical Corporation Process for production of (meth)acrylic compounds and method of distillation
JP4412019B2 (ja) * 2004-03-23 2010-02-10 三菱化学株式会社 （メタ）アクリル酸およびそのエステルの取り扱い装置の閉塞防止方法
FR2877003B1 (fr) * 2004-10-26 2007-01-05 Arkema Sa Procede ameliore de fabrication d'anhydride (meth) acrylique
FR2891841B1 (fr) * 2005-10-11 2007-12-28 Arkema Sa Melange odorisant pour combustible gazeux inodore
DE102009058058A1 (de) 2009-12-14 2011-06-16 Basf Se Verfahren zur Polymerisationsinhibierung von (Meth)acrylsäure und/oder Meth)acrylsäureestern
JP6489275B1 (ja) 2018-08-14 2019-03-27 セントラル硝子株式会社 含フッ素重合性単量体の蒸留精製法
CN114456070B (zh) * 2021-07-09 2024-05-14 广东华锦达新材科技有限公司 一种丙烯酸类物质分离过程中的阻聚方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE524422A (de) * 1952-11-20
NL101742C (de) * 1960-07-20
GB1265419A (de) * 1969-08-22 1972-03-01
JPS5761015B2 (de) 1974-01-16 1982-12-22 Nippon Shokubai Kagaku Kogyo Kk
US3964978A (en) * 1974-12-09 1976-06-22 Cosden Technology, Inc. NO2 polymerization inhibitor for vinyl aromatic compound distillation
US4338162A (en) * 1980-12-15 1982-07-06 The Dow Chemical Company Inhibitor for the polymerization of a 2-isocyanatoalkyl ester of an α,β-ethylenically unsaturated carboxylic acid
JPH0764788B2 (ja) * 1986-07-21 1995-07-12 三井東圧化学株式会社 ２−ヒドロキシアルキル（メタ）アクリレ−トの製造方法
JPH02248402A (ja) 1989-03-22 1990-10-04 Mitsubishi Petrochem Co Ltd アクリル酸エステル類の重合禁止剤及び重合禁止方法
ES2143067T3 (es) 1994-08-18 2000-05-01 Ici Plc Procedimiento para la preparacion de esteres acrilicos refinados.
US5545786C1 (en) * 1994-11-28 2001-10-16 Ciba Geigy Corp Method for inhibiting premature polymerization of vinyl aromatic monomers

Also Published As

Publication number Publication date
JP4131005B2 (ja) 2008-08-13
KR20020056945A (ko) 2002-07-10
JP2003532631A (ja) 2003-11-05
KR100520266B1 (ko) 2005-10-11
US7029556B1 (en) 2006-04-18
CN1399624A (zh) 2003-02-26
FR2801306B1 (fr) 2001-12-28
AU1712901A (en) 2001-06-04
EP1232138A1 (de) 2002-08-21
FR2801306A1 (fr) 2001-05-25
DE60023336D1 (de) 2006-03-02
DE60023336T2 (de) 2006-07-06
WO2001038285A1 (fr) 2001-05-31
CN1220670C (zh) 2005-09-28

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